KR101607354B1 - Sample injector - Google Patents

Abstract

The object of the present invention is to provide a technique for simplifying the structure of a sample injector for injecting a sample solution.
A sample injector 13 injecting a fixed amount of the sample solution S into the mobile phase solvent M and discharging the sample solution S together with the mobile phase solvent M. The sample injector 13 is provided with a solvent passage 42 for supplying a mobile phase solvent M and a rotating body 21 having a sample solution S passage for supplying the sample solution S and a fluid outlet 21 for discharging the mobile phase solvent M and the sample solution S to the outside And a second support member 23 having a side passage 34 formed therein. At least one of the rotating body 21 and the second supporting member 23 is configured so that the sample solution S room is communicated with the sample solution S passage so that the sample solution S is filled with the sample solution S through the sample solution S passage S charging position and a sample in which the sample solution S in the sample solution S room is injected into the mobile phase solvent M in which the sample solution S chamber communicates with the solvent passage 42 and the outlet side passage 34 and flows through the solvent passage 42 Solution S injection position.

Description

Sample injector {SAMPLE INJECTOR}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sample injector used for sample injection of chromatography using liquid or gas as a sample.

The sample injector used in liquid chromatography can generally be constructed using a flow path switching valve. The flow path switching valve appropriately switches the flow path of the mobile phase solvent and the flow path of the sample solution to realize the injection of the sample solution into the mobile phase solvent. Specifically, for example, FIG. 15 discloses a conventional example using a well-known hexane switching valve 99. The hexavalent exchange valve 99 has six ports of port numbers 1 to 6 and realizes two flow path states of charging (loading) the sample and injecting the sample.

At the time of filling the sample, two ports of port numbers 2 and 3 are connected, so that the flow path of the mobile phase solvent is connected to the column for separating the sample from the pump. At this time, since the two ports of port numbers 1 and 6 are also simultaneously connected, the flow path of the sample solution from the port of port number 4 through the sample loop 98 to the port of port number 6 (drain) is formed. Thereby, the remaining liquid can be discharged from the sample loop 98 while loading the sample solution into the sample loop 98 from the port of port number 4 by means of a syringe (not shown). On the other hand, at the time of injection, two ports of port numbers 1 and 2 are connected, and two ports of port numbers 3 and 4 are connected. As a result, a flow path is formed in which the sample loaded in the sample loop 98 flows backward by the discharge pressure from the pump and is injected into the column.

Such switching of the flow paths has been generally carried out by sliding two planes having a plurality of through holes in contact with each other and rotating them so as to switch the communicating state of a plurality of through holes between these planes Literature 1 to 4). On the other hand, the amount of the sample solution was measured based on the syringe to which the sample was injected or the amount of the surplus liquid.

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-25683 [Patent Document 2] Japanese Patent Application Laid-Open No. 8-5621 [Patent Document 3] Japanese Patent Application Laid-Open No. 2003-185645 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-121164

However, conventionally, in order to switch the communication state of the plurality of through holes by sliding, it is necessary to use a complicated mechanism with high precision and an elastic seal member for realizing such sliding movement, and as described above, Also needed. Such a complicated mechanism has been found by the present inventors that the number of parts is large and the burden of reassembling after cleaning is large and adjustment at that time is difficult and maintenance of initial performance is difficult. On the other hand, the inventors of the present invention have found that the use of the elastic seal member poses a problem of an increase in the number of parts, mixing of foreign matter, and short wear life.

SUMMARY OF THE INVENTION The present invention has been made in order to solve at least part of the above-described conventional problems, and it is an object of the present invention to provide a technique for simplifying the structure of a sample injector for injecting a sample solution.

Hereinafter, the effective means for solving the above-described problems will be described while showing effects and the like as necessary. In the following, corresponding configuration examples in the embodiments of the invention are appropriately shown in parentheses and the like for ease of understanding, but the present invention is not limited to the specific configurations shown by parentheses and the like.

<Means 1>

A sample injector (sample injector 13) for injecting a predetermined amount of sample (sample solution S) to the mobile phase medium (mobile phase solvent M) and discharging the sample together with the mobile phase medium,

A first member (rotating body 21) having a medium passage (solvent passage 42) for supplying the above-mentioned mobile phase medium and a sample passage for supplying the sample,

(A support member 23) provided in contact with the first member in a close contact state and provided with a discharge passage (outflow passage 34) for discharging the mobile medium and the sample to the outside,

Wherein the first member and the second member are in surface contact with each other and have relative sliding contact with each other, and at the same time, the medium passage and the sample passage of the first member and the discharge passage of the second member And an opening on the outer circumferential surface,

A sample chamber (concave chamber (44B, 44C)) into which the sample flows is formed in a concave shape on the outer circumferential surface of any one of the first member and the second member,

Wherein at least one of the first member and the second member has a sample filling position in which the sample chamber is communicated with the sample passage so that the sample is filled in the sample chamber through the sample passage, And is movable to a sample injection position where the sample in the sample chamber is injected into the mobile phase medium communicated with the discharge passage and flowing through the medium passage.

In the sample injector of the means 1, at least one of the first member and the second member is relatively movable to the sample filling position and the sample injection position. The sample filling position is a position where the sample chamber is communicated with the sample passage and the sample is filled in the sample chamber after passing through the sample passage. The sample chamber is formed in a concave shape on the outer peripheral surface of any one of the first member and the second member, and is a thread into which the sample flows. On the other hand, the sample injection position is a position where the sample chamber communicates with the medium passage and the discharge passage and the sample in the sample chamber is injected into the moving medium.

According to the above configuration, the sample can be filled in the sample chamber at the sample filling position, and the filled sample can be injected into the mobile phase medium at the sample injection position. As a result, it is possible to inject a predetermined amount of sample into the mobile medium, and to discharge the sample together with the mobile medium to the downstream side.

In addition, the communication between the passages may be such that the medium passage of the first member and the discharge passage of the sample passage and the second member are open to the outer peripheral surface of each member, and the outer peripheral surfaces of the first member and the second member, And the relative sliding movement is possible. According to the structure in which the contact surfaces of the two members are formed into an arc shape and the relative sliding movement is enabled in this way, the leakage from the contact surface can be appropriately managed. Therefore, for example, at least one of the complicated bearing mechanism and the elastic seal member It is possible to realize the switching of the flow path and the measurement of the sample injection amount. For this reason, it can be suitably used, for example, in a chromatography apparatus for feeding a mobile phase medium at a high pressure.

The outer circumferential surfaces of the arcuate surfaces are in surface contact with each other and the relative sliding movement is possible. The outer circumferential surface of the concave semicircular outer circumferential surface (also referred to as concave semicircular surface) and the convex semicircular outer circumferential surface Called radius of the surface pressure distribution can be varied to provide a design freedom of adjustment of the surface pressure distribution. Thus, according to the design specifications of the sample injector, the sealing performance in the communication of each flow path can be freely set. Specifically, for example, the following configuration is applicable.

When the radius of the concave half-moon-shaped surface is set to be smaller than the radius of the convex half-moon-shaped surface, the both half-moon-shaped surfaces are pressed against each other and brought into close contact with each other. Thereby, it is possible to realize a region in which a sufficient sealing performance (also referred to as seal performance) is secured without using an elastic seal member, for example, and the degree of freedom of designing the flow path (for example, the number of sample chambers) .

On the other hand, if the radius of the concave half-moon-shaped surface is set to be larger than the radius of the convex half-moon-shaped surface, it is possible to obtain a sharp peak in the innermost portion of the concave half- The surface pressure distribution can be realized. This is because the two half-moon-shaped surfaces are brought into close contact with each other by the large elastic deformation in the innermost portion of the concave half-moon-shaped surface. Such a configuration is problematic in that, for example, the pressure performance of the sealing performance is low because the pressure of the flow path for filling the sample is low, while the pressure of the flow path for injecting into the mobile medium at the sample injection position is remarkably high, This is a preferable configuration when performance is required. Further, a precise fitting tolerance may be used.

As described above, the means 1 has a structure in which the outer circumferential surfaces each having an arcuate shape are in surface contact with each other and the relative sliding movement is possible. Therefore, according to the design specifications of the sample injector, the sealing performance in the communication of each flow path can be freely set have.

<Means 2>

Wherein the sample chamber is provided in a plurality of directions along a relative moving direction of the first member and the second member.

According to the means 2, since a plurality of sample chambers are provided along the relative movement directions of the first member and the second member, the sample injection positions are set at a plurality of positions at different amounts of movement in the relative movement direction. In this case, the sample can be injected from the plurality of sample chambers by a simple operation such as relative movement of the first member and the second member.

<Means 3>

Wherein the plurality of sample chambers include sample chambers having different volumes from each other.

According to the means 3, the plurality of sample chambers include sample chambers having different volumes from each other, whereby samples having different volumes can be continuously injected.

<Means 4>

A medium chamber (concave chamber (44A)) into which the mobile phase medium is introduced is formed in the outer peripheral surface of any one of the first member and the second member in a concave shape,

At least one of the first member and the second member is moved to a medium outflow position where the medium chamber communicates with the medium passage and the discharge passage so that the moving medium in the medium passage flows out to the discharge passage via the medium chamber A sample injector according to any one of the preceding claims 1 to 3.

According to the means 4, the medium chamber formed on the outer circumferential surface of any one of the first member and the second member communicates with the medium passage and the discharge passage, and the medium in the medium passage flows out to the discharge passage via the medium chamber. To the outflow position. Since the sample chamber has the medium chamber in this way, it is possible to continuously supply only the mobile phase medium to the inspection vessel (column or the like) downstream of the sample injector using the medium chamber. Therefore, the conditioning of the inspection vessel, that is, the stabilization of the state of the mobile medium in the same inspection vessel, can be performed.

&Lt; Means 5 &

Wherein the sample chamber and the medium chamber are juxtaposed along the relative moving direction of the first member and the second member,

A groove portion having a length at a distance from the sample chamber and the media chamber is formed along the relative movement direction of the first member and the second member at the end portion on the outer peripheral surface of the medium passage in the first member Lt; RTI ID = 0.0 &gt; 4, &lt; / RTI &gt;

According to the means 5, at the outer circumferential surface side end portion of the medium passage, a groove portion having a length corresponding to the relative moving direction of the first member and the second member and at least a distance between the sample chamber and the media chamber. Thereby, even when the first member and the second member move relative to the medium outflow position or the sample injection position, the communication between the medium passage of the first member and the second member can be maintained through the groove portion.

&Lt; Means 6 &

(1) to (5) in which a recovery passage (sample outlet passage (45)) is provided in the first member so as to communicate with the sample chamber and which collects surplus of the sample filled in the sample chamber &Lt; / RTI &gt;

According to the means 6, when the relative positions of the first member and the second member are at the sample filling position, the surplus of the sample can be recovered through the recovery passage at the same time as the sample is charged into the sample chamber. Therefore, even if bubbles or the like are present in the sample chamber, it can be reliably charged without excluding it.

The recovery passage may be communicated when the sample passage is communicated with the sample chamber, and may be released when the communication passage is released.

<Means 7>

Wherein the outer peripheral surface of the first member has a curvature smaller than that of the outer peripheral surface of the second member.

According to the means 7, since the outer circumferential surface of the first member has a smaller curvature than the outer circumferential surface of the second member, the peak of the surface pressure distribution on the contact surface between the first member and the second member is alleviated Leakage can be suppressed in a wide area. Further, even if the relative position between the first member and the second member is largely changed, the state in which the leakage is suppressed can be maintained, and as a result, the relative amount of movement of the first member and the second member can be increased.

<Means 8>

And a third member (first supporting member (22)) for pressing and supporting the first member toward the second member is provided on the side opposite to the second member with the first member interposed therebetween, And the member is rotatably installed between the second member and the third member.

According to the means 8, since the first member can be pressed and supported by the second member side and the third member from both sides with the first member therebetween, simple support can be realized.

<Means 9>

Wherein an outer circumferential surface of the first member which is in contact with the second member and the third member is formed in a convex half-moon shape, and outer circumferential surfaces of the opposing second member and the third member are formed in a concave half-moon shape, Wherein the member is rotatably supported by the second member and the third member.

According to the means 9, since the outer circumferential surface of the first member can be constituted as a part of the circle, the first member can be simply manufactured with a shelf or the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a configuration of a high-speed chromatography apparatus according to an embodiment. FIG.
2 is an external view showing an appearance of an injector;
3 is an exploded perspective view showing the main components of the injector in an exploded state;
Fig. 4 is a cross-sectional view showing the main part of the injector cut, Fig. 4 (a) is a sectional view taken along the line AA in Fig. 2, and Fig.
FIG. 5 is a cross-sectional view greatly showing the flow path shape of the injector shown in FIG.
6 is a cross-sectional view greatly showing the flow path shape of the injector.
7 is a perspective view for explaining the flow path shape of the injector before injecting the sample.
8 is a schematic view for explaining the flow path of the injector before injecting the sample.
9 is a perspective view for explaining a flow path of an injector when a sample is injected;
10 is a perspective view for explaining a flow path shape of an injector when a sample is injected;
11 is a schematic view for explaining a flow path shape of an injector when a sample is injected.
12 is a perspective view for explaining a flow path shape of an injector when a sample is injected;
13 is a schematic view for explaining a flow path of an injector when a sample is injected.
FIG. 14 is an enlarged cross-sectional view showing the flow path of the injector at the time of injection in the modification. FIG.
15 is a schematic diagram showing a conventional flow path switching valve.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In this embodiment, a high-speed chromatographic apparatus for realizing high-performance liquid chromatography will be described.

(Configuration of High-Speed Chromatography Apparatus of A. Embodiment)

1 is a schematic diagram showing the configuration of a high-speed chromatography apparatus 18 according to an embodiment. High-performance liquid chromatography allows the mobile phase solvent M to pass through the column 15 at a high flow rate by mechanically applying a high pressure, thereby shortening the time during which the sample as an analyte stays in the stationary phase, thereby increasing separation ability and detection sensitivity . High-speed chromatography can be carried out automatically, for example, from the sampling of an analyte to the detection and quantification, so that highly reproducible analysis can be performed relatively easily. High-speed chromatography is frequently used in analytical chemistry or biochemistry.

The high-speed chromatography apparatus 18 includes a solvent storage bottle 10 for storing a mobile phase solvent M, a degassing apparatus 11, a pump 12, a sample injector (hereinafter referred to as an injector) 13, A column thermostatic chamber 14, a column 15 provided inside the column thermostatic chamber 14, a detector 16, and a recorder 17. The injector 13 has a sample filling function and a flow path switching function. After injecting the sample solution S, that is, after injecting the sample solution S into the sample chamber formed in the injector, the injector 13 switches the injector internal flow path, And is injected into the solvent M. The high-speed chromatographic apparatus 18 is a device for performing liquid column chromatography at a high speed by using a liquid as a mobile phase medium, filling a column with a stationary phase and enabling analysis of trace samples.

Each component of the high-speed chromatography apparatus 18 has the following functions. In the solvent storage bottle 10, a mobile phase solvent M is stored. The deaeration device 11 removes gas such as foam or dissolved oxygen from the mobile phase solvent M supplied from the solvent storage bottle 10. The pump 12 presses the mobile phase solvent M to a predetermined high pressure state and supplies the mobile phase solvent M in a high pressure state to the injector 13 via the solvent pipe 28. The injector 13 injects the sample solution S to be analyzed into the mobile phase solvent M and feeds the sample solution S together with the mobile phase solvent M to the column 15 through the solvent pipe 29 at a high pressure.

The column 15 has a filler (not shown) functioning as a stationary phase in a cylindrical container (not shown), and a reaction mixture dissolved in a solvent is flowed into the filler, and the affinity with the filler, The separation is carried out using the other. The column 15 is maintained at a predetermined temperature in the column thermostatic chamber 14. The detector 16 detects each separated material as an electric signal and transmits it to the recording system 17 as an electric signal. The solution that has passed through the detector 16 is discarded after being purified. The recorder 17 records the electric signal as time-series data and calculates the amount of each substance separated in the column 15 based on, for example, the peak value. Conversion to an electrical signal is performed using optical properties (absorbance, refractive index, fluorescence, etc.), electrochemical properties, or mass spectrometry.

As the mobile phase solvent M, various solvents can be used within a range that does not adversely affect the high-speed chromatography device 18 (particularly column (15)). Specifically, for example, aqueous solutions of water or salts, alcohols, acetonitrile, dichloromethane, trifluoroacetic acid and the like are used. In many cases, a solvent having compatibility (mixing with each other) is mixed and used. The analysis time in one sample supply to the column 15 varies greatly depending on the analytes and the analysis parameters, but generally requires several minutes to several tens of minutes for one analysis.

Types of analysis in high-speed chromatography include isocratic analysis and gragent analysis. Gragent analysis is a method of eluting by changing the composition of the solvent continuously. Specifically, for example, in the case of using a water / methanol gradient in reversed phase chromatography, first, a substance having a high polarity is eluted under a condition of low methanol, and then the proportion of methanol is increased, The less polar material is sequentially eluted.

Graz analysis has an advantage of high degree of freedom of separation, and also requires a time for conditioning in continuous analysis, thereby complicating the apparatus. On the other hand, isocratic analysis is a method of performing elution without changing the composition of the solvent. Has a disadvantage that the degree of freedom of separation is low. On the other hand, it is suitable for continuous analysis, and the apparatus can be simplified, and the analysis result is stable.

Next, the basic structure of the injector 13 will be described. Fig. 2 is a schematic view showing the configuration of the injector 13 in a state of being connected to the solvent pipes 28 and 29. Fig. The injector 13 is a mechanical component that injects the sample solution S into the mobile phase solvent M supplied from the solvent piping 28 and discharges the sample solution S together with the mobile phase solvent M to the solvent pipe 29.

The injector 13 has a cylindrical rotary body 21 for supplying and recovering the sample solution S and a pair of support members 22 and 23 provided between the rotary body 21, The rotating body 21 is held by the pair of supporting members 22 and 23 in such a state that the rotating body 21 is rotatable about its central axis A and is not displaceable in the axial direction. The supporting members 22 and 23 have a function of supporting the rotating body 21 in a rotatable state and a function of supplying the mobile phase solvent M to the rotating body 21 side (a function of introducing the mobile phase solvent M into the injector) , And has a function of discharging the mobile phase solvent M and the sample solution S to the downstream side of the injector. Also, for convenience of explanation, the support member 22 is referred to as a first support member 22, and the support member 23 is referred to as a second support member 23 as well. In the present embodiment, the rotating body 21 corresponds to the "first member" and the second supporting member 23 corresponds to the "second member".

The first support member 22 is connected to the solvent piping 28 through the joint member 24 and the second support member 23 is connected to the solvent piping 29 through the joint member 25. The support members 22 and 23 are brought into contact with the outer peripheral surface of the rotating body 21 in close contact with the joint members 24 and 25 provided with the injector 13 therebetween, A fixing member 26 is provided. The fixing member 26 may have any structure as long as it is capable of maintaining the close contact state between the rotating body 21 and the supporting members 22 and 23. However, It is preferable to have a fastening function by a screw or the like. The number of fixing members 26 may be arbitrarily set. The fixing member 26 may be configured to directly apply a pressing force to the support members 22 and 23 without passing through the joint members 24 and 25.

The rotating body 21 rotates relative to the support members 22 and 23 and functions as a flow path switching valve for switching the flow path of the sample solution S and the mobile phase solvent M. In other words, the injector 13 enables injection of the sample solution S by switching the flow path by the rotating body 21. [

Next, the configuration relating to the flow path switching of the injector 13 will be described in detail. 3 is an exploded perspective view showing the main components of the injector 13 in an exploded manner. 4 is a cross-sectional view of the main part of the injector. FIG. 4 (a) is a sectional view taken along the line A-A of FIG. 2, and FIG. 4 is a sectional view taken along the line B-B of FIG.

4, only the rotating body 21 and the supporting members 22 and 23 are shown. 5A and 5B are diagrams for explaining the arrangement and positional relationship of the passages provided in the rotator 21 and the support members 22 and 23. FIG 8A shows the contact surface of the first support member 22, (b) shows the contact surface of the rotating body 21 on the first support member 22 side, (c) the contact surface on the second support member 23 side of the rotating body 21, And the contact surfaces of the support member 23 are schematically shown.

3 and 4, the two support members 22 and 23 have a substantially columnar shape, and their axes are aligned in the direction orthogonal to the axis (central axis A) of the rotating body 21 And is set in the rotating body 21. In this case, arc-shaped concave portions 22a, 23a are formed in the portions of the support members 22, 23 that are in contact with the rotating body 21, and the outer peripheral surface of the concave portions 22a, Shaped surface formed in a half-moon shape concave to match the outer shape of the rotating body 21. That is, the outer circumferential surfaces of the rotary body 21 and the support members 22 and 23, which are in the form of arcs, are in surface contact with each other and relatively slidable. The radius of the arc of the concave portions 22a, 23a (half-moon-shaped surface) is smaller than the radius of the outer diameter of the rotating body 21. However, the circular arc radius of the recesses 22a, 23a may be the same as the outer radius of the rotating body 21, or the opposite relationship may be used.

The depth dimension of the concave portions 22a and 23a is smaller than the radius of the rotating body 21 so that a gap is formed between the two support members 22 and 23. The outer circumferential surface of the rotating body 21 and the concave surface of each of the support members 22 and 23 serve as sliding surfaces when the rotator 21 rotates with respect to the support members 22 and 23. [ In the present embodiment, the radii of the support members 22 and 23 (the radius of the cylindrical portion) are larger than the radius of the rotating body 21, but they may have the same configuration or opposite configurations. In addition, the outer shape of the support members 22 and 23 may be arbitrary or may be an angular column shape. The size and outer shape of the support members 22 and 23 may be different from each other.

The first support member 22 is provided with a first support member 22 and a second support member 22. The first support member 22 has a recess 22a at the center thereof, Side passage 31 for supplying M to the rotating body 21 side is formed. The concave portion 22a is formed with a groove portion 32 extending in the axial direction of the rotating body 21 from the outlet side end portion of the inlet side passage 31. [ 4 (a) and 4 (b), the inlet-side passages 31 are shown as solid lines, but the same inlet-side passages 31 are actually located inside .

An outflow passage 34 for discharging the mobile phase solvent M and the like to the solvent pipe 29 is formed in the central portion of the concave portion 23a of the second support member 23, that is, the innermost portion of the concave portion 23a . The concave portion 23a is provided with a groove portion 33 extending in the same axial direction at a position spaced apart from the inlet side end portion of the outflow passage 34 in the axial direction of the rotor 21, Two grooves 35 and 36 extending in parallel with each other and extending in the same circumferential direction are formed at positions spaced apart from each other in the circumferential direction of the inner circumferential surface of the concave portion with respect to the side passage 34 and the groove portion 33.

On the other hand, as shown in Figs. 3 and 4 (a), the rotating body 21 is provided with the solvent passage 42 so as to cross the center portion of the same rotating body 21. The outer circumferential surface of the rotating body 21 and the ends of the solvent passage 42 on the side of the first support member 22 and the end on the side of the second support member 23 are arranged in the circumferential direction of the rotating body 21 Grooves 41 and 43 are formed. The solvent passage 42 serves to discharge the mobile phase solvent M introduced from the inlet side passage 31 and the groove portion 32 of the first support member 22 into the groove portion 33 of the second support member 23 . In this case, since the groove portions 41 and 43 extending in the circumferential direction of the rotating body are provided at both ends of the solvent passage 42, even if the rotating body 21 rotates in the predetermined rotation angle range, The communicating state with the inlet passage 31 and the communicating state between the solvent passage 42 and the groove 33 are maintained.

The groove length (length in the circumferential direction of the rotating body) of the groove 43 is substantially equal to the groove length (length in the circumferential direction of the rotating body) of the groove portions 35 and 36 formed in the second support member 23 have. The groove length (the length in the axial direction of the rotating body) of the groove 33 previously formed in the second support member 23 is at least equal to the groove portion 36 on the side of the second support member 23 and the rotation body 21 And the groove 43 on the side of the outer circumferential surface of the outer circumferential surface.

3 and 4 (b), the rotating body 21 is provided with an introduction passage 48 for introducing the sample solution S supplied from the outside (a syringe or the like) A recovery passage 47 for recovering the surplus sample solution S is formed so as to extend in the axial direction of the rotating body 21. A sample inlet passage 46 for connecting one end of the same passage and the outer peripheral surface of the rotating body 21 is formed in the introducing passage 48. One end of the same passage and the other end of the rotating body 21 And a sample outlet passage 45 for connecting the outer circumferential surface of the sample outlet passage 45 is formed. The sample inlet passage 46 and the sample outlet passage 45 are arranged in the axial direction of the rotating body 21 and the outer circumferential ends of the sample inlet passage 46 and the sample outlet passage 45 are connected to the groove portions 35 and 36 formed in the second support member 23, It is communicating. In this case, the groove portions 35 and 36 are provided so as to extend in the circumferential direction of the inner circumferential surface of the concave portion. Therefore, even if the rotating body 21 rotates in the predetermined rotation angle range, 36 and the communicating state between the sample outlet passage 45 and the groove 35 are maintained.

Concave recesses 44A, 44B, and 44C are formed on the outer circumferential surface of the rotating body 21 and are parallel to each other and extend in the axial direction of the rotating body 21, respectively. In Fig. 3, for convenience of explanation, the recessed chambers 44A to 44C are provided with a mesh hanger. These concave chambers 44A to 44C form a space of a predetermined volume between the concave portions 44A to 44C and the concave surface of the second support member 23. [ The volumes of the concave chambers 44A to 44C may be equal to each other or may include at least two different volumes. In the present embodiment, the volumes of the recessed chambers 44A to 44C are all the same. The recessed chambers 44A to 44C are each formed to have a length that can extend over the outflow passage 34 and the groove portion 33 and also over the two groove portions 35 and 36 The groove length is the same). The recessed chambers 44A to 44C are formed in a direction extending in the direction intersecting the groove portions 35 and 36 formed in the second support member 23 (in the direction orthogonal to the present embodiment).

The three concave chambers 44A to 44C are spaced apart from each other in accordance with the length of the groove portion 43 (downstream groove portion) communicating with the solvent passage 42, and the concave chamber 44A, The recessed chamber 44B is located on the side of the center of the groove 43 and the recessed chamber 44C is located on the side of the groove 43 (the side in the axial direction, the same in the following) at one end of the groove 43 At the side of the other end of each of the first and second side walls.

When the rotating body 21 rotates, the concave chamber 44 (any one of 44A to 44C) is in the following state with the rotation thereof.

(1) A state in which the concave chamber 44 extends over the outflow passage 34 and the groove 33.

(2) The state in which the concave chamber 44 extends over the two groove portions 35 and 36.

(3) A state in which the concave chamber 44 is not extended to any of the outflow passage 34, the groove portion 33, and the groove portions 35 and 36.

In this case, in the state (1), the mobile phase solvent M (high-pressure solvent) flows in the order of the solvent passage 42 → the groove 43 → the groove 33 → the concave chamber 44 → the outflow passage 34 . In the state (2), the sample solution S flows in the order of the sample inlet passage 46 → the groove portion 36 → the concave chamber 44 → the groove portion 35 → the sample outlet passage 45. In the state (2), the sample solution S is filled in the concave chamber 44 and the sample solution S is continuously flowed into and out of the concave chamber 44. Therefore, Even if bubbles or foreign substances are present in the sample solution 44, the bubbles and foreign substances can be discharged to the outside by being loaded on the flow of the sample solution S. Further, in the state (3), neither the mobile phase solvent M nor the sample solution S flows into and out of the recessed chamber 44. In the case of (3) above, if the sample solution S is already filled in the concave chamber 44, the sample filling state is maintained.

In the configuration of the present embodiment, when the recessed chamber 44A is set to the state of (1), for example, among the three recessed chambers 44A to 44C, the other recessed chambers 44B and 44C (2) above. That is, when filling the sample solution S with respect to the concave chambers 44B and 44C, the filling path is made independent from the flow path of the mobile phase solvent M, and the mobile phase solvent M is mixed with the concave chambers 44B and 44C, . Therefore, the introduction of the mobile phase solvent M to one concave chamber 44 (for example, the concave chamber 44A) and the introduction of the other concave chamber 44 (for example, the concave chamber 44B, 44C) can be carried out simultaneously with the introduction of the sample solution S.

In the present embodiment, the state in which the concave chamber 44A is the above (2) and the other concave chambers 44B and 44C are the above (1) is referred to as an initial state, that is, . From this initial state, the rotating body 21 is rotated in a predetermined direction, whereby sample injection into the mobile phase solvent M is sequentially performed on the charged sample solution S in the concave chambers 44B and 44C.

The groove portions 35 and 36 are formed to extend in the circumferential direction of the rotating body 21 so that the sample solution S can be simultaneously introduced into both the concave chambers 44B and 44C.

As described above, the injector 13 is configured so that the outer circumferential surfaces each having an arc shape are in surface contact with each other and relatively slidable in the flow path switching between the rotating body 21 and the support members 22, 23 have. According to such a configuration, leakage from the contact surface can be appropriately managed, so that switching of the flow path and measurement of sample injection amount can be realized without using a highly accurate rotation mechanism and an elastic seal member. For this reason, it can be suitably used, for example, in a chromatography apparatus for feeding a mobile phase medium at a high pressure.

The outer circumferential surfaces of the respective arcuate surfaces are in surface contact with each other and the relative sliding movement is enabled. The outer circumferential surfaces 22a and 23a (also referred to as a concave semicircular surface) and the convex semicircular outer circumferential surface It is possible to provide a degree of freedom of design in which the surface pressure distribution is adjusted by changing the radii of the convex portions 21a (also referred to as convex halftone surfaces). Thus, according to the design specifications of the sample injector, the sealing performance in the communication of each flow path can be freely set. Specifically, for example, the following configuration is applicable.

When the radii of the concave half-moon-shaped surfaces 22a and 23a are set to be smaller than the radius of the convex half-moon-shaped surface 21a, the both half-moon-shaped surfaces are pressed against each other and brought into close contact with each other. Thereby, it is possible to realize a region in which a sufficient sealing performance (also referred to as seal performance) is secured without using an elastic seal member, for example, and the degree of freedom of designing the flow path (for example, the number of sample chambers) .

Conversely, if the radius of the concave half-moon-shaped surfaces 22a, 23a is set larger than the radius of the convex half-moon-shaped surface 21a, the innermost part of the concave half- A surface pressure distribution having a sharp peak can be realized. This is because the two half-moon-shaped surfaces are brought into close contact by the large elastic deformation in the innermost portions of the concave half-moon-shaped surfaces 22a, 23a. Such a configuration is preferable when, for example, the pressure of the flow path for filling the sample is low and the required performance of the sealing performance is low, and the flow path pressure for injection into the mobile medium at the sample injection position is remarkably high. Further, a precise fitting tolerance may be used.

As described above, the present embodiment has a configuration in which the outer circumferential surfaces each having an arc shape are in surface contact with each other and the relative sliding movement is possible. Therefore, the sealing performance in the communication of each flow path can be freely set It is possible.

In order to relatively position the rotating body 21 in the direction of the central axis A (rotational axis) relative to the supporting members 22, 23 with respect to at least one of the rotating body 21 and the supporting member 22, (Not shown). In this way, positioning of the respective members in the axial direction can be realized simply.

The rotating body 21 and the supporting members 22 and 23 are formed by laser microfabrication on a ceramic material for example through holes such as the holes 31, 42 and 34 and concave portions 32, 41, 33 and the like. However, the material and the processing method are not limited thereto, and may be a metal material such as silicon carbide SiC or stainless steel, or may be processed by other usable processing methods.

(B. Operation of high-speed chromatography apparatus)

Next, the operation of the high-speed chromatography apparatus 18 will be described, focusing on the operation of the injector 13. Here, the flow path shape of the injector 13 is roughly divided into four states, and the four flow path shapes are shown as (a) to (d) in FIG. 6 (a) to 6 (d) show a state in which the rotating body 21 is slightly rotated in the clockwise direction in the drawing .

6A shows the initial state of the injector 13 and shows a state in which the sample inlet passage 46 communicates with one end side of the groove portion 36 and one of the three concave chambers 44A to 44C The other recessed chambers 44B and 44C are located at positions where the recessed chambers 44A communicate with the outlet side passages 34 and communicate with the groove portions 36. [ 6 (b) to 6 (d), the communicating position is changed, but the communicating state is maintained.

6B shows a state in which the recessed chambers 44A and 44B out of the three recessed chambers 44A to 44C are not in communication with any of the outflow passage 34 and the recessed portion 36, (44C) is in a position to communicate with the groove portion (36). After this, the concave chamber 44A remains in a state where it does not communicate with any of the outflow-side passage 34 and the groove portion 36. [

6C shows a state in which only the concave chamber 44C communicates with the groove 36 at a position where the concave chamber 44B communicates with the outflow passage 34 among the three concave chambers 44A to 44C And is in a state of being in a position. 6D is a state in which the concave chamber 44C is in a position where it communicates with the outflow passage 34 out of the three concave chambers 44A to 44C.

Each of the above states can be switched appropriately depending on the stage in which the injector 13 is in the sample injection step. Hereinafter, the operation will be described in detail at each stage such as before sample injection and sample injection.

6A shows the state in which the rotating body 21 is in the "medium outflow position of the concave chamber 44A and the sample filling position of the concave chamber 44B, 44C" 6C shows a state in which the rotating body 21 is at the sample injection position of the concave chamber 44B and at the sample filling position of the concave chamber 44C and FIG. And the whole 21 is in the &quot; sample injection position of the concave chamber 44C &quot;.

(Before B-1 sample injection)

The flow path shape of the injector 13 before injecting the sample solution S will be described with reference to Figs. 7 and 8. Fig. 7 is a perspective view for explaining the flow path shape of the injector 13 before sample injection. Fig. 8 is a schematic view for explaining the flow path shape of the injector 13 before injecting the sample. Fig. 8 (a) is a schematic view seen from a direction orthogonal to the axial direction of the rotary body, and Fig. 8 .

6 (a). In this state, in the three concave chambers 44A to 44C, the mobile phase solvent M flows through the concave chamber 44A and the other concave chambers 44A, And the sample solution S flows through the inward seals 44B and 44C. At this time, the mobile phase solvent M (high-pressure solvent) flows along the solvent flow path formed in the order of the solvent passage 42 → the groove portion 43 → the groove portion 33 → the concave chamber 44A → the outflow passage 34. That is, only the mobile phase solvent M is discharged from the injector 13 to the solvent pipe 29, and the mobile phase solvent M is supplied to the downstream side column 15. In the column 15, the conditioning (state adjustment) of the inside of the column is performed by the mobile phase solvent M supplied from the injector 13. Thereby, the state inside the column can be stabilized, and the preparations before the sample inspection can be performed.

The sample solution S flows in the order of the sample inlet passage 46 → the groove portion 36 → the concave chambers 44B and 44C → the groove portion 35 → the sample outlet passage 45. Thus, a predetermined amount of the sample solution S is filled in both the concave chambers 44B and 44C.

(B-2. Sample injection)

Next, the flow path shape of the injector 13 at the time of injecting the sample solution S will be explained with reference to Figs. 9 to 13. Fig. Here, a series of flows shown in Figs. 6 (b) to 6 (d) will be described. Figs. 9, 10, and 12 are perspective views for explaining the flow path shape of the injector 13 at the time of injecting the sample, which corresponds to Fig. 7 described above. Figs. 11 and 13 are schematic diagrams for explaining the flow path shape of the injector 13 when injecting the sample in the same manner, which corresponds to the above-described Fig. 8. Fig.

In the case of injecting the sample, the rotating body 21 is first shifted from the state of FIG. 6 (a) to the state of FIG. 6 (b). In this case, the state shown in FIG. 9 is reached, and the flow of the mobile phase solvent M using the recessed chamber 44A is ended and the sample filling is completed for the recessed chamber 44B.

Thereafter, the rotating body 21 is rotated again to move to the state of Fig. 6 (c). 10 and Fig. 11, so that the sample solution S filled in the concave chamber 44B is injected into the mobile phase solvent M flowing in the solvent flow path, and the sample solution S together with the mobile phase solvent M is injected into the downstream side Column side). At this time, since the sample solution S is metered in a predetermined amount in the state of being filled in the concave chamber 44B, the sample filling amount can be specified accurately without performing additional metering.

In the present embodiment, the outflow passage 34 of the support member 23 is formed as a very fine hole with a diameter of 25 mu m. This is because, when discharging the sample solution S, mixing of a small amount of the sample solution S into the mobile phase solvent M of the order of a few nanometers can be suppressed. However, since the fine holes 34 are difficult to be elongated due to processing problems, the recess 37 is formed to shorten the length of the outflow-side passage 34 to a processable length L.

In the present embodiment, the mobile phase solvent M continues to flow continuously after the sample solution S is injected. Thereby, in the isocratic analysis, the sample solution S is discharged from the column 15, and the conditioning of the column 15 is completed in a short time.

After the completion of the first sample injection, the rotating body 21 is rotated again to move to the state shown in Fig. 6 (d), and the second sample injection is performed. 12 and Fig. 13, so that the sample solution S filled in the concave chamber 44C is injected into the mobile phase solvent M flowing in the solvent flow path, and the phase of the mobile phase solvent M The sample solution S is discharged to the downstream side (column side).

Since the concave chamber 44C can be configured to fill more sample solution than the concave chamber 44B, for example, different amounts of the sample solution S can be continuously injected in a short time.

In this manner, the injector 13 of the present embodiment can perform two successive analyzes in a short time, for example, in the isocratic analysis. In addition, the degree of freedom of measurement such as the amount of the sample solution S injected or the number of times of continuous injection can be easily improved.

Also, the method of analysis need not necessarily be an isocratic analysis. However, the idosquadratic analysis is advantageous in that it can be continuously measured in a short time, and therefore, it is an analytical method suitable for the present embodiment.

Further, although two concave chambers 44B and 44C are connected in parallel between the grooves 35 and 36 in the above-described configuration example, one or more concave chambers 44B and 44C may be used. All of the recessed chambers 44 may have the same volume (filling capacity), some of the recessed chambers 44 may have the same volume, and the other recessed chambers 44 may have different volumes.

(D. Variation Example)

Further, the present invention is not limited to the description of each embodiment described above. For example, the following description is also applicable.

(a) In the above-described embodiment, the two rows of grooves 35 and 36 are formed as grooves of the same and uniform width extending in the circumferential direction. However, for example, as shown in Fig. 14, at the position where the sample outlet passage 45 and the sample inlet passage 46 are connected to each other, the same width of the width W2 is provided, and the position where the two concave chambers 44B and 44C are connected The width of the recovery concave portion 35 may be narrowed to W3.

By doing so, the interval between the grooves 35, 36 can be made wider, so that the length L of the two recessed chambers 44B, 44C is made longer without increasing the length of the bridge d, can do. From the viewpoint of ensuring the filling of the sample solution S, it is preferable that the distance d is not more than twice the length in the width direction (the direction perpendicular to the direction of the length L) of the groove-like concave portion, preferably not more than 1 time .

In addition, when the concave chambers 44B and 44C have significantly different amounts of overlapping, it is also possible to maintain an appropriate trapezoid d by partially adjusting the widths of the distribution concave portion 36 and the recovery concave portion 35. [

(b) Although the concave chambers 44A, 443, and 44C are formed on the side of the rotating body 21 in the above-described embodiment, they may be formed on the side of the support member 22, for example. In this configuration, two rows of grooves 35 and 36 and grooves 33 are formed on the side of the rotating body 21, and grooves 43 are formed on the side of the supporting member 22. [

It should be noted, however, that the above-described embodiment is advantageous in that the measurement variables can be simply changed by preparing plural types of rotors 21 having different numbers of concave chambers 44A, 44B, 44C and different loading capacities, .

(c) In the embodiment described above, two rows of grooves 35, 36 are provided on one side of the groove 33 in the circumferential direction, but may be provided on both sides of the groove 33 in the circumferential direction. In this way, the sample solution S can be loaded and injected for each reciprocating operation of the rotation operation, and the charging and the injecting are alternately repeated. Thereby, efficient operation becomes possible.

(d) In the above embodiment, the rotating body 21 as the first member is formed in a columnar shape, but it may not be a cylindrical shape. The rotating body 21 may have an arc-shaped contact surface with the support members 22 and 23 and be rotatable in a state of being supported by the support members 22 and 23. The shape of the other portions may be arbitrary .

(e) In the above embodiment, the first member (the rotating body 21 in the above embodiment) in which the medium passage and the sample passage are formed, the second member provided in contact with the first member in intimate contact with the discharge passage, The second member may be fixed to the second support member 23 in the above-described embodiment, and the first member may be moved relative to the second member. However, it may be modified such that the first member is fixed and the second member is moved relative to the first member. It is also possible to configure both the first member and the second member to be movable, and to adjust the relative movement amounts of both members.

It is also possible to form the contact surface on the first member side in a concave shape and the contact surface on the second member side in a convex shape.

(f) The relative movement direction of the first member and the second member is not limited to the circumferential direction about the rotational axis but may be the axial direction of the rotational shaft. In this case, since the relative movement directions of the both members are changed by 90 degrees in the plan view, the arrangements of the flow paths provided in the rotating body 21 and the supporting members 22 and 23 are changed by 90 degrees ( In which case rotation is not necessary). Also in this configuration, it is possible to switch the flow of the fuel in the injector 13 in the same manner as described above.

(g) In the above embodiment, the present invention is embodied in a liquid chromatographic apparatus using a mobile phase solvent M as a mobile phase medium. Instead, the present invention can be applied to a gas chromatography apparatus using a gas as a mobile phase medium.

10: solvent storage bottle
11: Deaerator
12: Pump
13: injector
14: Column thermostat
15: Column
16: detector
17: Recorder
18: High performance chromatographic apparatus
21: Rotor (first member)
21a:
22: first supporting member (third member)
22a:
23: second supporting member (second member)
23a:
34: Outlet passage (discharge passage)
42: Solvent passage (medium passage)
43:
44A: Concave chamber (medium chamber)
44B, 44C: concave chamber (sample chamber)
45: sample outlet passage (return passage)
46: Sample inlet passage (sample passage)
47:
48: introduction passage (sample passage)
M: Mobile phase solvent (mobile phase medium)
S: Sample solution (sample)

Claims (9)

A sample injector for injecting a predetermined amount of sample to a mobile medium and discharging the sample together with the mobile medium,
A first member having a medium passage for supplying the mobile phase medium and a sample passage for supplying the sample,
And a second member provided in contact with the first member in a close contact state and having a discharge passage for discharging the mobile phase medium and the sample to the outside,
Wherein the first member and the second member are in surface contact with each other and have relative sliding contact with each other, and at the same time, the medium passage and the sample passage of the first member and the discharge passage of the second member And an opening on the outer circumferential surface,
Wherein a sample chamber into which the sample flows is formed in a concave shape on the outer circumferential surface of any one of the first member and the second member,
Wherein at least one of the first member and the second member has a sample filling position in which the sample chamber is communicated with the sample passage so that the sample is filled in the sample chamber through the sample passage, Wherein the sample injector is movable to a sample injection position in which the sample in the sample chamber is injected into the mobile phase medium communicated with the discharge passage and flowing through the medium passage. The sample injector according to claim 1, wherein a plurality of sample chambers are provided along the directions of relative movement of the first member and the second member. The sample injector according to claim 2, wherein the plurality of sample chambers include sample chambers having different volumes from each other. 4. The apparatus according to any one of claims 1 to 3, wherein a medium chamber into which the mobile phase medium is introduced is formed in a concave shape on the outer circumferential surface of any one of the first member and the second member,
At least one of the first member and the second member is moved to a medium outflow position where the medium chamber communicates with the medium passage and the discharge passage so that the moving medium in the medium passage flows out to the discharge passage via the medium chamber Possible, sample injectors. The apparatus according to claim 4, wherein the sample chamber and the medium chamber are juxtaposed along the relative movement direction of the first member and the second member,
A groove portion having a length at a distance from the sample chamber and the media chamber is formed along the relative movement direction of the first member and the second member at the end portion on the outer peripheral surface of the medium passage in the first member The sample injector, located. The sample injector according to claim 1, wherein the first member is provided with a recovery passage communicably connected to the sample chamber, for collecting surplus of the sample filled in the sample chamber. The sample injector according to claim 1, wherein the outer peripheral surface of the first member has a smaller curvature than the outer peripheral surface of the second member. 2. The image forming apparatus according to claim 1, wherein a third member for pressing and supporting the first member to the second member side is provided on the side opposite to the second member with the first member interposed therebetween, The first member being rotatably mounted between the second member and the third member. 9. The image forming apparatus according to claim 8, wherein an outer circumferential surface of the first member contacting the second member and the third member is formed in a convex half-moon shape, and an outer circumferential surface of the opposing second member and the third member is concave And the first member is rotatably supported by the second member and the third member.

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